Synthesis of Ternary Homogeneous

Azeotropic Distillation
Sequences: 2. Flowsheet Identification
Sutijan *,1
Megan Jobson 2
Robin Smith 2
1
Department of Chemical Engineering, Faculty of Engineering, Gadjah Mada University, Jl.
Grafika 2 Yogyakarta, Indonesia
2
School of Chemical Engineering and Analytical Science, The University of Manchester, PO
Box 88, Sackville St, Manchester, M60 1QD, UK
*
e-mail : sutijan@chemeng.ugm.ac.id

This paper presents a systematic methodology for flowsheet generation for

separating binary azeotropic mixtures using homogeneous azeotropic distillation. A new
classification system for ternary mixtures using ‘standard distillation line maps’ defined in
Sutijan et al. (2012) is employed. The new characterisation system is able to link candidate
entrainers to flowsheet structures which can facilitate the separation. The sequences
considered include pressure-swing distillation, two and three-column flowsheets with or
without boundary crossing and the use of single and double-feed columns. For a given
ternary mixture, suitable flowsheet structures that can facilitate the separation can be
automatically identified. The method is illustrated using examples.

Keywords: Azeotropic distillation, Entrainer selection, Residue curve map, Distillation line
map, Distillation sequence, Flowsheet structures

INTRODUCTION sequences and can be used to screen

potential entrainers. The two types of maps
Recent research on ternary azeotropic are qualitatively identical (Widagdo and
distillation has addressed entrainer Seider, 1996). Therefore they provide
selection, flowsheet synthesis and column valuable conceptual tools for process
design, including that for two-feed synthesis, that is, for selecting a suitable
columns. An understanding of the entrainer, flowsheet configuration and
applicability and limitations of existing columns designs, to separate a binary
methods allows outstanding problems for mixture in the presence of an entrainer.
flowsheet synthesis to be identified. Depending on the structure of ternary
Residue curve and distillation line maps mixtures, various flowsheet alternatives to
are useful for assessing the feasibility of separate binary azeotropic mixtures have
proposed distillation columns and column been proposed. Doherty and Caldarola
44 Synthesis of Ternary Homogeneous Azeotropic Distillation Sequences: 2. Flowsheet Identification
(1985) and Foucher et al. (1991) have
studied the flowsheet for the separation of
ternary azeotropic mixtures without
distillation boundaries. Knapp and Doherty
(1992) apply the concept of pressure swing
distillation for the separation of binary
azeotropic mixtures by considering the use
of entrainers that produce distillation
boundaries. Stichlmair and Herguijuela
(1992) propose the ‘generalised flowsheet’
for separating the constituents of minimum
or maximum-boiling azeotrope using
entrainers that produce distillation
boundaries. The generalised flowsheet
contains three columns and two recycle
streams. Generally, the flowsheet structures
proposed are limited to certain class of
distillation line maps, and therefore, can
miss other promising entrainers.
This work proposed a systematic
methodology for generation of feasible
flowsheet configuration for separating
binary azeotropic mixtures by use of
entrainers. The vapour-liquid equilibrium
behaviour of ternary homogeneous
mixtures is characterised using a ‘standard
distillation line maps’ which can explicitly
make a link between proposed entrainers,
the feasibility of the desired separation
between the binary azeotrope-forming
components and the distillation sequence
and recycle connections (flowsheet
structure) that will facilitate the separation.
Associated with each entrainer facilitating
the desired separation is one or more
flowsheets. A systematic approach to
linking proposed entrainers to suitable
flowsheets is developed.
BACKGROUND
The sequence synthesis problem for
separating ternary homogeneous
azeotropic mixtures consists of selecting
the distillation sequence, the associated
recycle structure and the flow rates and
compositions of all streams such that the
proposed flowsheet and the columns it
contains are feasible, and preferably also
economically attractive. The flowsheet is
feasible if composition profiles of all
columns are continuous, i.e. there is
intersection between rectifying and
stripping section composition profiles for a
single-feed column.
Rooks et al. (1998) propose the ‘common
saddle criterion’ to identify feasible splits
using a single-feed column. The feasibility
criterion requires the high-reflux or high-
reboil liquid composition profiles from both
products to approach the same saddle. This
criterion is a sufficient (but not necessary)
condition for split feasibility that can miss
other feasible splits. In particular, when
‘continuous distillation regions’ (Safrit and
Westerberg, 1997), also known as
‘compartments’ (Thong, 2000) exist,
feasible splits can be incorrectly identified
as unfeasible splits.
Stichlmair and Herguijuela (1992)
propose the ‘generalised flowsheet’ for
separating the constituents of an a-b
minimum- or maximum-boiling azeotrope
using an entrainer. The generalised
flowsheet requires the distillation boundary
to be curved; one of the columns crosses
the distillation boundary. The generalised
 Sutijan, Megan Jobson, and Robin Smith 45

flowsheet contains three columns and two transfer rates. Feasibility is tested using
recycle streams. If the boundary is highly pinch point curves and distillation lines or
curved a two-column flowsheet can be residue curves (Wahnschafft et al., 1992);
used. the feasibility test is extended to consider
The set of feasible composition profiles product compositions specified in terms of
of a column section is bounded by the total a desired purity. The recycle composition is
reflux and minimum reflux (reversible selected using a trial and error procedure.
operating) composition profiles No guidance for general flowsheet
(Wahnschafft et al., 1992) i.e. the residue synthesis is given.
curve and pinch point curve passing This work presents a systematic method
through the product composition. These for identifying promising flowsheets for the
regions form the basis of a feasibility test: If separation of binary azeotropic mixtures.
the bounds of the composition profiles do Promising entrainers are identified using a
not intersect or overlap, the two proposed new classification of ternary mixtures
products cannot be obtained in a single- ‘standard distillation line maps’ developed
feed column. This concept is an extension in Sutijan et al. (2012) which is able to link
of the one proposed by Levy et al. (1985), candidate entrainers to flowsheet
who uses the intersection of liquid structures.
composition profiles for the two proposed
products as a criterion for feasibility. IDENTIFICATION OF FEASIBLE
Knapp and Doherty (1992) extend the FLOWSHEET CANDIDATES
concept of pressure swing distillation for
the separation of binary azeotropic An entrainer is said to be feasible if there
mixtures by considering the use of an is at least one flowsheet structure that can
entrainer, which is known as ‘pressure facilitate the separation of a given binary
shifting’. Pressure-insensitive binary azeotropic mixture. Flowsheet features
azeotropes can be separated using include boundary shifting or crossing,
entrainers that produce pressure-sensitive recycling and mixing, and the use of two-
distillation boundaries. The composition feed columns. Depending on the
space may contain multiple distillation characteristics of the distillation line map
boundaries; as long as only one boundary (i.e. product stability and the existence of
separates the desired products, a two- distillation boundaries), one or more
column configuration can be used to flowsheet structures can be associated with
separate binary mixtures using boundary each standard distillation line map
shifting. associated with feasible entrainers.
Castillo et al. (1998b) propose a When an entrainer does not introduce a
sequence of design procedure for ternary distillation boundary between the two
azeotropic distillation based on graphical desired products, recycles in a two-column
analysis. For a given ternary mixture, flowsheet (i.e. without boundary shifting or
flowsheets can be proposed that shift or crossing) can generally facilitate the
cross the boundary or exploit finite mass separation. For single-feed column
46 Synthesis of Ternary Homogeneous Azeotropic Distillation Sequences: 2. Flowsheet Identification

Table 1. Feasible flowsheets for the separation of a binary azeotrope for which the entrainer
does not introduce a distillation boundary between the saddle- and node-type products. A
two-column flowsheet with recycle can facilitate the separation.
Azeotrope Type Direct sequence Indirect sequence

Maximum-boiling

Minimum-boiling

flowsheets, both the direct and the indirect
sequence can be used (see Table 1),
although both sequences may not be
feasible for a given standard distillation line
map. The common saddle criterion (Rooks
et al., 1998) provides guidance about which
specifications are feasible.
Figure 1 shows an example of an
entrainer that does not introduce a
distillation boundary. A two-column
flowsheet with recycles (Fig.1) can facilitate
the separation of the minimum-boiling
butyl acetate-butanol azeotrope using
either the direct or indirect sequence. The
specifications of column C-1a (Fig.1a)
satisfy the common saddle criterion. At
high reflux ratios, the rectifying and
stripping profiles approach the same
saddle (1-octene). This column is
potentially feasible. The specifications of
column C-1b (Fig. 1a) do not satisfy the
common saddle criterion. At high reflux
ratios, the stripping profile approaches the
azeotrope (stable node), so this column is
generally unfeasible.
Many entrainers do not introduce a
distillation boundary between two saddle
products, but cause the composition space
to contain two ‘continuous distillation
regions’ (Safrit and Westerberg, 1997) or
‘compartments’ (Thong, 2000). Fig. 2
illustrates a distillation line map containing
two compartments, namely regions 2-3-4
and 1-3-4. The behaviour of residue curves
and distillation lines within a compartment
is analogous to that of a zeotropic ternary
mixture, in which the volatility order is fixed.
That is, the compartment represents a
relatively well-behaved composition
subspace.
It is possible for single-feed columns to
cross compartment boundaries – i.e. for the
two products to lie in different
compartments (Thong and Jobson, 2000b).
However, the region of feasible product
compositions is generally very small. It is
 Sutijan, Megan Jobson, and Robin Smith 47

butanol, 117.9 °C
1 direction of
rectifying profile D1 D2
0.8 116°C direction of
stripping profile
0.6
C-2 feed 1 2
0.4

C-1b
0.2 C-1a

0
B1 B2
0 0.2 0.4 0.6 0.8 1
1-octene, 121.3°C butyl acetate, 126.1°C

butyl acetate, 126.1°C

1

D1 D2
0.8

C-2 feed
0.6
1 2
0.4
116°C
0.2 C-1
B1 B2
0
0 0.2 0.4 0.6 0.8 1
1-octene, 121.3°C butanol, 117.9 °C

Fig. 1: Two-column flowsheet (a) Indirect sequence (primary product is butyl acetate):
Column C-1a, which satisfies the common saddle criterion, is feasible, whereas column C-
1b is generally unfeasible. (P=1 atm); (b) Direct sequence(primary product is butanol): Both
column specifications satisfy the common saddle criterion. (P=1 atm).

generally only relatively easy to obtain a Butyl acetate, 126.1 °C

2
distillate and a bottom product with 1 Azeotrope : unstable node
Entrainer : stable node

compositions close to the stable and 0.8

unstable nodes, respectively, as illustrated 0.6

in Fig. 2. This restriction is due to the fact 0.4

harder split

that the composition profiles do not have Azeotrope, 116.0°C

0.2 4
to traverse far into the adjacent 3 1
compartment to intersect (Fig. 3). As the
0
0 0.2 0.4 0.6 0.8 1
1-Pentanol, 138°C Butanol, 117.9°C
products move away from stable and
Fig. 2: Cross-compartment splits in a
unstable nodes, single-feed columns
single-feed column.
become unfeasible (Fig. 4). In these cases, a
two-feed column can facilitate the
separation. The middle-section Thong (2000b) noted that, in a single-
composition profile can bridge the gap feed column, the intersection of the
between the stripping and rectifying pinch point curves is a necessary condition
composition profiles. for split feasibility. That is, if the products
48 Synthesis of Ternary Homogeneous Azeotropic Distillation Sequences: 2. Flowsheet Identification

cannot be produced from a reversible Table 2 summarises the flowsheet

column, these products cannot be structures using single-feed columns that
produced at all. Thong (2000b) also can be used to obtain saddle-type final
observed that compartment boundaries products.
can only be crossed in one direction. For Butyl acetate, 126.1 °C
example, in Fig. 5, some 24/13 splits are 1

feasible, while 14/23 splits never are. (A 0.8

rectifying section
composition profile

24/13 split is a separation where one 0.6 stripping section

product composition lies close to the

composition profile

0.4
composition space boundary between D
pinch point
Azeotrope, 116.0°C

singular points 2 (butyl acetate) and 4

curves
0.2

(butyl acetate-butanol azeotrope) and the

B
0
0 0.2 0.4 0.6 0.8 1
other product composition lies close to the 1-Pentanol, 138°C Butanol, 117.9°C

composition space boundary between Fig. 4: An unfeasible cross-compartment

singular points 1 (butanol) and 3 (1- split in a single-feed column. The
pentanol) (Thong and Jobson, 2000a). A product compositions are located far
24/13 split is analogously defined.) from the stable and unstable nodes.
Butyl acetate, 126.1 °C
Butyl acetate, 126.1 °C 1 2 Azeotrope : unstable node
Entrainer : stable node
1
0.8

0.8
rectifying section 0.6
composition profile
0.6 feasible split
0.4
D Azeotrope, 116.0°C
stripping section
0.4 B' 4
composition profile D'
0.2
Azeotrope, 116.0°C unfeasible split
D B 1
0.2 0
pinch point 03 0.2 0.4 0.6 0.8 1
curves 1-Pentanol, 138°C Butanol, 117.9°C
0
0 B
Fig. 5: Feasible and unfeasible
0.2 0.4 0.6 0.8 1
1-Pentanol, 138°C Butanol, 117.9°C

Fig. 3: A feasible cross-compartment directions of splits for a single-feed

split in a single-feed column. The column that crosses a compartment
compositions of both products are boundary.
located close to the stable and unstable
Thong (2000b) proposed tests for
nodes.
classes of splits for predicting the feasibility
Since some single-feed columns can of cross-compartment splits using two-
cross a compartment boundary, flowsheets feed columns. These tests were based on
containing such columns can allow saddle- the VLE behaviour at the compartment
type final products to be obtained. This boundary. He also proposed that a given
result introduces a set of candidate class of split (Thong and Jobson, 2000a) can
entrainers that are not accommodated by be performed in a two-feed column if and
existing entrainer selection criteria. only if it can also be performed in a single-
To employ a single-feed column that feed column. That is, whether a class of
crosses a compartment boundary, a three- split is feasible (e.g. 24/13 or 14/23, as
column flowsheet is generally needed.
 Sutijan, Megan Jobson, and Robin Smith 49

Table 2. Feasible flowsheets using single-feed columns for the separation of a binary
azeotropic mixture where the entrainer does not introduce a distillation boundary between
the two saddle-type products. Column 2 crosses a compartment boundary.
Azeotrope Type Single-feed column

Maximum boiling

Minimum boiling

acetate-chlorobenzene mixture, as shown

in Fig. 6. Because two-feed columns can
recover saddle-type final products (e.g.
ethanol), two-column flowsheets can
facilitate the desired separation, as
summarised in Table 3.
Classical extractive distillation is a well-
known example of a two-column flowsheet,
where the two-feed column produces a
Fig. 6: Two-feed column producing a
saddle-type final product. In this case, a
saddle type product. Middle profile is
heavy entrainer is used to separate a
required to bridge the gap between
minimum-boiling azeotrope. The entrainer
stripping and rectifying operation
introduces neither distillation boundaries
leaves. The split is always unfeasible in a
nor new azeotropes, i.e. class OOA type C.
single-feed column.
Laroche et al. (1991) propose a graphical
technique to determine the order of
shown in Fig. 12) applies equally to single-
recovery of products in the extractive
feed and double-feed columns. While the
distillation flowsheet. They propose that
product compositions of single-feed
component A must be recovered first if the
columns are constrained to lie close to the
A-B isovolatility curve terminates on the A
unstable and stable nodes, a two-feed
axis. This technique only applies to classical
column is not similarly constrained. For
extractive distillation (OOA type C) but not
example, a high-purity ethanol distillate
more generally to two-column flowsheets
could be obtained from an ethanol-ethyl
50 Synthesis of Ternary Homogeneous Azeotropic Distillation Sequences: 2. Flowsheet Identification

using a two-feed column that crosses a their relatively low boiling temperatures
compartment boundary. and latent heats of evaporation.
When a distillation boundary exists
Table 3. Feasible flowsheets for the
between the two components to be
separation of binary azeotrope for which
separated, the products lie in different
entrainers do not introduce a distillation
distillation regions. In general, two-column
boundary between two saddle-type
flowsheets using only recycle without
products. The two-feed column crosses a
boundary crossing or boundary shifting
compartment boundary.
cannot recover the desired products since
Azeotrope Type Double-feed
at least one intermediate product must be
column
in the same distillation region as another
column. Laroche et al. (1992) demonstrate
Maximum
that it is possible to cross a distillation
boiling
boundary by introducing the feed to a
column in one region, and by recovering
the products in an adjacent region
(boundary crossing). Knapp and Doherty
Minimum
(1992) demonstrate the use of two columns
boiling
operated at different pressures to recover
two products which lie in different
distillation regions (boundary shifting).
The concept of extractive distillation can
Flowsheets employing boundary crossing,
be generalised and can allow a new set of
boundary shifting or recycling and mixing
candidate entrainers to be defined. These
can recover pure component products
entrainers may introduce new azeotropes
which are separated by a distillation
with one or both of the components to be
boundary.
separated and may also introduce
Boundary shifting (Knapp and Doherty,
distillation boundaries in the distillation line
1992) can be applied for both straight and
map. Fig. 3 presents the set of standard
curved boundaries. Pressure-sensitive
distillation line maps for such entrainers.
distillation boundaries can allow relatively
For separating minimum-boiling
low recycle-to-feed ratios to be used, even
azeotropes, entrainers may be low-boiling
if new azeotropes appear as a result of the
compounds (e.g., class XXA type C(5) and
pressure change. Fig. 7 illustrates a feasible
XXA type C(6)), intermediate-boiling
two-column flowsheet for such a case. As
compounds (e.g., class XXA type C(5), XXA
shown in Fig. 13, if no new azeotrope were
type C(6), AOA type C, OAA type C, OAX-Y
formed, a higher recycle-to-feed ratio
type C and AOX-Y type C) or high-boiling
would be required. The relative flows of
compounds (e.g., class OOA type C, OOX-Y
recycles D2 (when a new azeotrope forms)
type C, XXA type C(5) and XXA type C(6)).
and D2 (when no new azeotrope forms) can
Intermediate- and low-boiling entrainers
be determined using the lever-arm rule.
can offer economic advantages because of
Three-column flowsheets exploiting
 Sutijan, Megan Jobson, and Robin Smith 51

boundary shifting can benefit from the In distillation line maps with a boundary
appearance of a new azeotrope in a similar separating two desired node-type
way. products, two-column flowsheets using
boundary shifting or three-column
flowsheets using boundary crossing or
recycling and mixing can always facilitate
the separation of the binary azeotropic
mixtures.
Fig. 8 presents the flowsheet mass
balance for a three-column flowsheet using
boundary shifting. As shown in Fig. 9, when
column C-2 is fed to the column C-3, all
Fig. 7: Two-column flowsheet with
columns satisfy the common saddle
boundary shifting. An entrainer that
criterion. That is, for high reflux ratios in
introduces a new azeotrope can reduce
column C-2, the stripping profile will
the recycle-to-feed ratio, relative to the
case that no new azeotrope is formed.
ethyl acetate
1 B3 Column C-1 at P1
Column C-2 at P2
Column C-3 at P2
In flowsheets featuring boundary 0.8 B2
C-3
azeotrope at P1
crossing, curvature of the boundary is 0.6
C-2 D 3 azeotrope at P2
exploited to allow the products of one feed
0.4
column to be located in different distillation D1 mixing line
region to the feed. More highly curved 0.2
C-1
boundaries can allow lower recycle-to-feed D2
0
B1
0 0.2 0.4 0.6 0.8 1
ratios than straighter boundaries (Castillo, MTBE tert-butanol
1997). However, reflux ratios and heats of Fig. 8: Three-column flowsheet using
vaporisation can also have a significant boundary shifting for the separation of
impact on the process economics, so minimum boiling binary azeotrope. The
entrainer selection on the basis of bottom product of column C-2 is fed to
boundary curvature alone is not adequate. the last column.
ethyl acetate
1
direction of stripping
B2 profiles
0.8
D1 D2 D3
0.6 direction of
rectifying
C-2 profiles
0.4

0.2

D2 B1 B2 B3
0
0 0.2 0.4 0.6 0.8 1
MTBE tert-butanol

Fig. 9: Direction of stripping and rectifying profiles for column C-2 when the bottom
product of column C-2 is fed to the last column. The product specifications satisfy common
saddle criterion. Both profiles approach the saddle at high reflux ratio. Flowsheet is feasible.
52 Synthesis of Ternary Homogeneous Azeotropic Distillation Sequences: 2. Flowsheet Identification

Table 4. Feasible flowsheets for the separation of a binary azeotrope where the entrainer
introduces a distillation boundary between the two node-type desired products.
Azeotrope Type Boundary Shifting/Crossing Recycling and Mixing

Maximum-boiling

Minimum-boiling

approach the saddle (azeotrope at P2), as line map where the two desired products
will the rectifying profile. are nodes separated by a distillation
When column C-3 is fed by the overhead boundary. The compositions of the feed to
product of column C-2, on the other hand, the process determine which flowsheets are
column C-2 will not satisfy the common feasible. If the feed is located on the
saddle criterion: at high reflux ratios, the convex side of the boundary, a three-
stripping profiles will approach the pure column flowsheet with boundary crossing
entrainer saddle and the rectifying profiles cannot perform the separation; a two-
will approach the pure ethyl acetate saddle, column flowsheet with boundary shifting
as shown in Fig. 10. Such product should be used, especially when the
specifications are generally unfeasible. boundary is pressure sensitive. When the
Table 4 summarises the flowsheet boundary is not pressure sensitive, the
alternatives for the classes of distillation three-column flowsheet with recycling and

ethyl acetate
1 direction of
rectifying profile

0.8

direction of D1 D2 D3
0.6 B2 stripping profile

0.4 C-2

0.2
D2 B1
0 B2 B3
0 0.2 0.4 0.6 0.8 1
MTBE tert-butanol

Fig. 10: Direction of stripping and rectifying profiles for column C-2 when the top product
of column C-2 is fed to the last column. The profiles approach the different saddles at high
reflux ratio. The flowsheet is unfeasible.
 Sutijan, Megan Jobson, and Robin Smith 53

Table 5. Feasible flowsheets for producing a node- and a saddle-type pure component
product separated by a distillation boundary using single-feed columns. Column C-2
crosses a compartment boundary
Azeotrope Single-feed column
Type

Maximum
boiling

Minimum
boiling

mixing could be used. summarises the feasible flowsheets

If one of the desired products is a saddle containing single-feed columns that can
and the other is a node, and a boundary facilitate the separation.
separates the products (classes XOX type butyl acetate

A(5) and OXX type B(6)), two compartments 1

will exist in one of the distillation regions.

direction of stripping
0.8 profile for column C-1

Since the two products are located in

direction of rectifying
0.6 profile for column C-1

different distillation regions, boundary 0.4

D1 feed
node azeotrope
(1 atm)

crossing, boundary shifting or recycling node azeotrope

(3 atm)
0.2
and mixing can allow recovery of the C-1
B1
products. In general, two single-feed
0
0 0.2 0.4 0.6 0.8 1
2-methyl-1-butanol butanol
columns with boundary shifting cannot
Fig. 11: An unfeasible flowsheet of two
perform the separation, as one of the
single-feed columns exploiting
columns, which has to produce a saddle
boundary shifting. Column C-1 lies in
product, must cross a compartment
the direction of unfeasible splits and
boundary. As illustrated in Fig. 11, this
does not satisfy the common saddle
column (column C-1) is unfeasible since it
criterion. Both profiles approach node
lies in the direction of unfeasible splits, as
type azeotrope at high reflux ratios.
discussed previously. However, three-
column flowsheets using single-feed
columns can perform the separation, as For distillation line maps of class XOX
column C-2 can cross the compartment type A(5) and OXX type B(6), flowsheets
boundary in the direction of feasible splits. using a two-feed column and recycling and
Fig. 12 illustrates such a flowsheet. Table 5 mixing or boundary shifting can perform
54 Synthesis of Ternary Homogeneous Azeotropic Distillation Sequences: 2. Flowsheet Identification

butyl acetate
1 B3

0.8 D1 D2

0.6 C-3
feed 1 2 3
0.4 D2

C-2 D3 azeotrope
0.2 B1 B2 B3
B1 B2 C-1 D1
0
0 0.2 0.4 0.6 0.8 1
2-methyl-1-butanol butanol

Fig. 12: Feasible flowsheet with three single-feed columns using recycling and mixing.
Column C-2 lies in the direction of feasible splits.

the separation. The composition space distillation region containing

contains two distillation regions, one of compartments, boundary shifting must be
which is similar to that for classical used. Otherwise, boundary shifting or
extractive distillation, i.e.; the distillation recycling and mixing can be used to
region contains two non-adjacent saddle facilitate the separation.
singular points. In the distillation region The feasible flowsheets for the
containing compartments (e.g. the region separation of a maximum-boiling
1-3-4-5 in Fig.13), a two-feed column must azeotrope are analogous to those for
be used to recover one desired pure separating a minimum-boiling azeotrope.
product and an intermediate product. The Table 6 summarises the flowsheets that can
flowsheet uses boundary shifting or be used to recover a saddle-type product
recycling and mixing, to recover the other and a node-type product using a two-feed
pure component product. Figs. Examples column, together with boundary shifting or
of such flowsheets are presented in Figures recycling and mixing.
13 and 14. When the feed is located in the
butyl acetate
1 B3 D3
D1 D2
2
0.8

0.6
C-3
5
0.4 B1 B2 B3
D2 4
D3 azeotrope (1 atm)
0.2 B1 feed
C-2 azeotrope (3 atm)
3 C-1
B2 1
0
0 0.2 0.4 0.6 0.8 D1 1
2-methyl-1-butanol butanol

Fig. 13: Three-column flowsheet using a two-feed column and boundary shifting. The feed
is located in the distillation region containing compartments (region 1-3-4-5). (P1=1 atm,
P2=1 atm, P3=3 atm)
 Sutijan, Megan Jobson, and Robin Smith 55

butyl acetate
1 B3 D3
2 D1 D2

0.8

0.6 C-3
feed

0.4 5 D2 feed

C-2 D3 azeotrope B1 B2 B3
0.2 B1 4
C-1 1
3 B2 D1
0
0 0.2 0.4 0.6 0.8 1
2-methyl-1-butanol butanol

Fig. 14: Three-column flowsheet using a two-feed column and recycling and mixing. The
feed is located in the distillation region without compartments (region 2-4-5). (P=1 atm).

DEPENDENCE OF FLOWSHEET When the azeotropic feed is rich in acetone,

STRUCTURES UPON THE CHOICE OF
PRIMARY AND SECONDARY PRODUCTS
The new classification
distillation line maps requires the primary
and secondary products to be defined. The
order in which the desired products are
recovered affects
structures are feasible. Figures 15 and 16
illustrate how the choice of primary
product can affect which flowsheets are
feasible for a given separation requirement.
An acetone-chloroform mixture is to be
separated using benzene as the entrainer.
chloroform
1 D3
a three-column flowsheet with boundary
crossing or a two-column flowsheet with
boundary shifting can facilitate the
system for separation. For the two-column flowsheet,
either acetone or chloroform can be
recovered as the primary product. However,
for the three-column flowsheet, acetone
which flowsheet must be recovered as the primary product.
Similarly, when the azeotropic feed is
rich in chloroform, a two-column flowsheet
with boundary shifting can facilitate the
separation. Either acetone or chloroform
can be recovered as the primary product.
However, a three-column flowsheet with
acetone
1 D3

C-3
0.8
D2 B3 0.8
azeotrope
C-3
0.6 distillation
C-2 0.6 boundary
D2

distillation line Feed m ixing line

0.4 boundary 0.4 azeotrope
B1 mixing line
m ixing line
C-2
0.2 B3 feed
B2 C-1 0.2
B1
D1 D1
B2 C-1
0 0
0 0.2 0.4 0.6 0.8 1 0 0.2 0.4 0.6 0.8 1
benzene acetone benzene chloroform
(a) (b)

Fig. 15: Three-column flowsheets for the separation of an acetone-chloroform mixture

using benzene as the entrainer (P=1 atm). (a) Feed is rich in acetone. Acetone is recovered
as the primary product when using boundary crossing. (b) The feed is rich in chloroform.
Chloroform is recovered as the primary product when recylcing and mixing are used.
56 Synthesis of Ternary Homogeneous Azeotropic Distillation Sequences: 2. Flowsheet Identification

boundary crossing cannot perform the considered; e.g. do the most difficult
separation, but the three-column separation last, favour the direct
arrangement using recycling and mixing sequence, remove first a component
can (Fig. 15b). In this case, there are three comprising a large fraction of the feed
recycled streams, which is likely to be and favour near-equimolar splits
economically unattractive. between the top and bottom products
The choice of which component is in a column.
recovered as the primary product should  Practical considerations (e.g. hazardous,
be made to benefit the process economics. reactive, heat sensitive and corrosive
The following guidelines are proposed for component must be recovered first)
the selection of the primary product: (Smith, 1995) can also suggest which
 The primary product should be selected product to recover first.
to result in a low recycle-to-feed ratio Since the guidelines are not clearcut, it
and/or few recycle streams. may be necessary to compare all possible
 Established heuristics (King, 1980) for flowsheets for both choices of primary
sequence selection should be product.

Table 6. Feasible flowsheets containing a two-feed column for the separation of a binary
azeotropic mixture using an entrainer that introduces a distillation boundary between the
saddle-type and node-type desired products
Azeotrope
Class Boundary Shifting Recycling and Mixing
Type

Minimum

XOX type
A(5)

Maximum

Minimum

OXX type
B(6)
Maximum
 Sutijan, Megan Jobson, and Robin Smith 57

chloroform
D2 acetone
1
1 D2

0.8 azeotrope at P 1
azeotrope at P 2 0.8

0.6
B1 0.6 feed
feed
0.4 B2
0.4 azeotrope at P1
distillation
boundary azeotrope at P2
distillation
0.2 0.2
B1
boundary
D1 B2 D1
0 0
0 0.2 0.4 0.6 0.8 1 0 0.2 0.4 0.6 0.8 1
benzene acetone benzene chloroform

Fig. 16: Two-column flowsheet using boundary shifting separates an acetone-chloroform

mixture using benzene as the entrainer (P1= 10 atm, P2= 1 atm). The binary feed is rich in
acetone. (a) Acetone is recovered as the primary product. (b) Chloroform is recovered as
the primary product.

ILLUSTRATIVE EXAMPLE the associated flowsheets are selected

Refer to the case study in Sutijan et al.
(2012), this example
separation of a mixture of acetone and
chloroform, in which components form a
maximum-boiling azeotrope.
feed mixture, is to be purified using
homogeneous azeotropic distillation. Since
the azeotrope composition is pressure-
insensitive, binary
distillation is not a cost-effective design
option. An entrainer is needed to facilitate
the separation. Promising entrainers and
according to the new methodology.
Suitable flowsheets for each entrainer are
addresses the identified directly, given the standard
distillation line map classification (see
Tables 1 to 6 in Sutijan et al. (2012). Figure
The binary 8 and Tables 2 (Sutijan et al., 2012) present
the eight entrainers to be considered. The
set of flowsheets that are suitable for each
acceptable entrainer is obtained directly
pressure-swing once the ternary mixtures have been
classified. Of the candidate entrainers, only
methanol is not suitable: in this case the
two products would be both saddles

Table 7. Feasible and unfeasible flowsheets for the separation of acetone-chloroform

mixtures (: feasible flowsheets ; N: cannot perform the separation).
Double- Double-
Boundary Boundary Recycling - Recycling
Entrainer feed (two feed (three
shifting crossing mixing only
columns) columns)
Acetic acid  N  N N N
Acrylic acid  N  N N N
Benzene   N N N N
F6 Acetyl acetone N N N N  N
Methyl ethyl
  N N N N
ketone
Thio acetic acid  N  N N N
Toluene   N N N N
58 Synthesis of Ternary Homogeneous Azeotropic Distillation Sequences: 2. Flowsheet Identification

separated by a distillation boundary. Table flowsheets with boundary shifting are

7 lists various feasible flowsheet expected to be an expensive option
configurations that can separate acetone - because the distillation boundaries for
chloroform binary azeotropic mixture. these mixtures are not pressure-sensitive
Various flowsheet configurations are and a large pressure difference will be
defined in Table 8. required if the recycle flow rate is not to be
When the binary feed is located on the excessive.
convex side of the boundary (entrainer is Thio acetic acid forms a straight
acetic acid or acrylic acid) only the two- distillation boundary. Flowsheets with
column flowsheet with boundary shifting boundary shifting or recycling and mixing,
and the three-column flowsheets with but not boundary crossing, can facilitate
boundary shifting or recycling and mixing the separation. For this pressure-
can facilitate the separation. The three- insensitive distillation boundary, a large
column flowsheet with recycling and pressure difference will be required to
mixing is expected to require large provide a low recycle-to-feed ratio. Overall,
columns, as the three recycled streams this entrainer is not expected to be a good
would result in relatively high feed flow entrainer.
rates to the columns, and, in turn, high F6 acetyl acetone does not introduce a
capital and operating costs for the distillation boundary between the two
flowsheet. However, reflux ratio is also an components to be separated. A two-feed
important design parameter, which column (extractive distillation) and
depends on other parameters such as flowsheets with three single-feed columns
column pressure, feed quality and can perform the separation. When using a
sharpness of the split. Therefore, the two-feed column, recycle-to-feed ratios
overall performance of the flowsheet can that can lead to feasible design depend on
only be judged after design and the vapour-liquid equilibrium behaviour of
optimisation. Two- or three-column the system. The distillation line map or

Table 8. Key to the definition of flowsheet structures used in this work

Cases Conditions
 Boundary exists
Boundary shifting  Different pressures applied
 No column crossing boundary
 Boundary exists
Boundary crossing  No pressure difference
 One of columns crossing boundary
 Boundary exists
 No pressure difference
Recycling and mixing  No column crossing boundary
 Boundary is crossed by mean of mixing between two streams
 No boundary exists
 No pressure difference
Recycling  No column crossing boundary
 No boundary crossing by mean of mixing between two streams
 Sutijan, Megan Jobson, and Robin Smith 59

residue curve map alone does not allow the
potential of this flowsheet to be evaluated
prior to design and optimisation.
Benzene, toluene and methyl ethyl
ketone all form a very curved distillation
boundary. Boundary crossing can facilitate
the separation; low recycle-to-feed ratios at
atmospheric pressure can be used.
Boundary shifting can also be used; in this
case, the gap between the two boundaries
can further improve the performance of the
flowsheet. For higher pressure differences,
the recycle-to-feed ratio is less, but so is the
volatility of the light key component,
relative to the heavy key component, in the
high-pressure column. This trade-offs
means that the operating conditions for
each entrainer must be optimised before
the entrainers can be compared.
CONCLUSIONS
the azeotropic feed to the process. The
approach to flowsheet identification is
systematic, providing one or more suitable
flowsheets for each promising entrainer.
The entrainer selection and flowsheet
identification procedure requires only the
small amount of data that is required to
determine the structure of the distillation
line map. The procedures are suitable for
implementation in computer-aided process
design software. The methodology is
therefore valuable and powerful for the
synthesis of ternary homogeneous
azeotropic distillation processes.
ACKNOWLEDGEMENTS
The authors thank the Engineering
Education Development Project of
Indonesia for their financial support of Dr
Sutijan.

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